Process for the dyeing of cellulosic materials and dyestuff preparations suitable for this purpose



s1. Jigs-6t Patented Dec. 15, 1953 UNITED STATES PROCESS FOR THE DYEINGF CELLULOSIC Q MATERIALS AND DYESTUFF PREPARA- TIONS SUITABLE FOR THISPURPO SE v KarlMenzi, Henri Riat; and Jacques Wegmann Basel,Switzerland, assignors to Ciba Limited Basel, Switzerland, a Swiss firmI N0 Drawing. Application July 20,1950,-

Serial No. 175,014 6 Claims priority, application Switzerland 1 Thepresent invention is based on the observation that cellulosic materialsare dyed in a valuable manner when the dyeing is carried out with ametal compound, diflicultly soluble per se, of a direct dyeing azodyestuff'which contains in complex combination one of the metals withthe atomic numbers 27 to 29, or with a mixture for the formationthereof, in the presence of an ali- Phatic base free from acid groups,whichcontains at least one basic nitrogen atom and at least one hydroxylgroup separated from the basic nitrogen atom by two carbon atoms,'whichbase is solid and water-soluble. I The metal compounds which aredifllcultly soluble in water per se contain in complex combination oneof the metals with'the atomic numbers 27 to 29, that is to say, in theorder of'increasing importance, cobalt, nickel "and copper: Espe-'-cially valuable results are obtaianed with such azo dyestuffscontainin'g copper as in the metal-free condition are still solubleinwater and suitable for the dyeing of cellulosic materials; but whichin the form of copper compounds are difllcultly soluble in water and onaccount of this property are not of good suitability for dyeing, atallevents when it is not intended to dye from a suspension,

which method as a rule'yields unsatisfactory results. In the presentcase those complex metal compounds-which give colloidal solutions inwater are also to be considered as diflicultly soluble. It is the resultof experience that these metal compounds are also unsuitable per se fordyeing on account of their very poor capacity for drawing onto thefiber. r

The diflicultly water-soluble dyestufis to be employed according to thepresent process, may for example be metal complexes of dyestuffs witho-hydroxy carboxylic acidgrouplngsas are present among others insalicylicacid. In this connection there should also be mentioned metalcomplexes of dyestuffs with the atom grouping As especially advantageoushave proved among others metal compounds of oto -dihydroxyazo dyestuffs,that is to say from dyestufl s w hich contain the atom grouping I I I iI a,

14 Claims.

(Cl. 8-42) 4 Also among the metal ompounds of o: o-'dihy'- droxyazodyestuffs the copper compounds are chiefly of value. These contain theatom grouping which is usually illustrated by the formula I o-N=Nc p 10at least once in the molecule. They can contain the atom grouping forexample twice and in the following form Z 3 Cu ",0" o \ON=N The coppercompounds of such constituti'onwhich are difiicultly soluble toinsolublein water can be produced by customary methods known, especiallyfor the production of water-soluble copper compounds, by treatmentwithage'nts providing copper of the corresponding metal-free azody'estuffs which contain the atom grouping In the case of azo dyestufis withthe last-mentioned grouping the treatment with agents providing coppershould ..be carried out in such a manner that the coppercomplex'formation'takes place with splitting 'ofi of the -O-alkyl group.

In some cases this takes place also with dyestuffs which yielddifllcultly s'olublecopper compounds,

by heating with copper tetrammine compounds of ammonia in an alkalinemedium for a prolonged period. Particularly effective ishowever in this40 case the application of the process of U. S. Patent applicationSerial No.778,734 (now U. S. Patent No. 2,536,957) t In general it isadvantageous to employ or produce the complex metal compounds for thedye- 5 stuff preparations in such a condition that their ionogenicsalt-forming groups, that is to say especially sulfonic-acid andcarboxyl groups (insofar as the latter are not used in the complexformation) exist in the form 01. metal salts, for example alkali metalsalts'and not as free acid groups or ammonium salts.

Instead of the complex metalcompounds there can also be used in thepresentprocess the mixtures used in the formation thereof. It is thuspossible for example "to employ a dyestuff free 3 from complex-formingmetal, suitably in the form of an alkali salt, in combination with thenecessary quantity of an agent providing metal. As agents providingmetal there are also concerned in this case the compounds known per sewhich' are normally used for the production of complex metal compounds.When" as agents providing metal simply constituted metal salts areemployed, as for example sulfates, nitrates or acetates, it is ingeneral advantageous to add to the dyebaths in addition to the-metalsalts further suitable additions which during the dyeing are capable ofdispersing any metal hydroxide produced. As an example of such anaddition'may Y be mentioned the sodium salt of N-rnethyl-;r- 4

analogous manner to that described in German Patent No. 635,904'bycondensation of hydroxy- V alkylamines with dihalogenalkyls.

heptadecyl-benzimidazole sulfonic-acldr" There may be used withadvantage as agents providing metal such compounds of complex-,1

forming metals as contain the metal in complex combination in the anion.In any case the complex formers should not possess the property ofwithdrawing metal from the complex metal com pounds of dyes'tuils underthe working conditions concerned. As examples of useful complex formersmay be mentioned aliphatic hydroxy carboxylic acids such as glycollicacid, lactic acid, fl-hydroxypropionic acid, e-hydroxybutyric acid,tartaric acid and citric acid.

It is to be recommended to employ a certain excess of the agentproviding metal over the theoretically necessary quantity.

According to the present invention the dyeing with the complex metalcompounds of the above described composition takes place in the presenceof an aliphatic base. This base contains at least one basic nitrogenatom and is solid, that is to say its melting point lies above thetemperatures at which the preparations are normally stored; it istherefore higher than 40 C. The base is in addition water-soluble andtree from acid groups such as 'sulfonic acid groups and carboxyl groups;on the other hand it contains at least one bydroxyl group,gwhich isseparated from the basic nitrogen atom by two "carbon atoms. ofart'ic'ularly good suitability are the bases of the composition I'MQ-H1, =(NHCCHr-OH):

in which R1 indicates a hydrogen atom, an 'alkyl group with at the mostthree carbon atoms or a hydroxymethyl grounRz a hydrogen atom or amethyl group and n awhole number 'whichiis 'at the most 4 but preferably2. I

Asexamples may be mentioned the bases of the following composition:

HCHr-'CHr-NH- CH1 HO-CHr-CHg-NH- H CH: HO'CHr-YH-NHCH Ho-ourcn-NrF m M.P. 136 to 139' C.

CHI CHI sno-onr-o-inn-onl HO-ClI G NH- n,

G l CH3 I M. P. 177 to 181' C.

- quantity proportion between the complex metal compound or the mixturefor the forma- 'tion thereoi'arid the organic base is in the presentprocesswith advantage so selected that a considerable excess of the baseis present, that is to say for one atom of complex-bound metal severalmolecules of base are present, for example more than two 'or a stillhigher number.

The present invention renders it possible to dye on cellulosic fibersdirectly in a single bath and a single stage process, as complex metalcompounds, without adding further materials to the dyebath apart fromthe customary auxiliary agents in the direct dyeing process such assodium sulfate and/or sodium carbonate, direct dyeing azo dyestuffs ofwhich the metal complexes are per se difiicultly soluble in water andwhich thereforegare unsuitable for dyeing as complex metal compounds,for which reason they are usually employed in the metal-free conditionand are only converted into the metal compounds when they are at leastfor the most part fixed on the fiber. The bath ratio, that is to say theratio of the quantity of the material to be dyed to the quantity of thedye liquor can in this case be varied within wide limits and canbesuited to a far-reaching extent to the requirements of practice. Ifdesired, as is customary in practice, prior to the preparation of thedyebaths, concentrated solutions, so-called stock solutions, can beformed with the base and the complex; metal, compound or with the base.the metal-free dyestufi and the agent providing metal, which solutionsare then' diluted to the larger volumes necessary for dyeing.

According to the present process there are obtained in this manner as arule dyeings which as regards color strength, purity of the dye shadeand fastness properties are at least equivalent to and in part aresuperior to those dyeings which are obtained when a correspondingquantity-of dyestuffs free from metals and bases is dyed by theafter-metallisation process.

In certain cases it may further be of advantage .to after-treat dyeingsobtainable according to the present process with such agents as increasetheir wet fastness properties. This after-treatment can also take placein the presence of agents providing copper. As products which improvethe wet fastness'properties of dyeing there may be mentioned amongothers the products of the action of formaldehyde on compounds such ascyanamide, dicyandiamide, dicyandiamidine, melamine and so on. Suchafter-treating agents are also concerned, in the production of which noformaldehyde is used. The application of after-treating agentscontaining copper is to be recommended especially when there areindications that during the dyeing a more or less farreachingde-coppering takes place.

Instead of bringing together the base and the complex metal compound orthe base, the metalfree dyestufi and the agent providing metal, in thedyebath or in one of the previously mentioned, so-called stocksolutions, it is to be recommended in general to work up the materialsconcerned to dry or if desired paste preparations. These new dyestuffpreparations, suitable for carrying out the initially described dyeingprocess, accordingly contain a metal compound of a direct dyeing azodyestufi, which compound per se is difficultly soluble and whichcontains in complex combination one of the metals with the atomicnumbers 27 to 29, or a mixture for the formation thereof, and alsocontain an aliphatic base free from acid groups, which contains at leastone basic nitrogen atom and atleast one hydroxyl group separated fromthe basic nitrogen atom by two carbon atoms and which base is solid,water-soluble and capable of imparting solubility to the complex metalcompounds.

The dyestuif preparations are suitably produced by mixing the individualrequired components, for example in the dry state. They can however alsobe produced in the moist condition, for example in paste form or bycombination of solutions or by association of moist or dissolvedcomponents of the mixture with dry components of the mixture followed ifdesired by drying. In the production of the dyestuff preparations by thewet method it is possible that preparations may be obtained in which atleast a portion of the complex metal compound of the dyestuif hasundergone chemical combination with the base. The preparations can alsobe subjected to admixture with further substances, such as urea orwater-soluble carbohydrates, for example saccharose. On the other handit is in general less to be recommended to incorporate in largequantities electrolytes such as sodium sulfate or sodium chloride. 4

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated and the relationbetween parts by weight and parts by volume being the same as thatbetween the kilogram and the liter. Where the production of dyebaths andstock solutions is described, as water preferably sodyelng results ofgood fastness to light and very ood fastness towashins.

- The same result is obtained when the 1:2-di(phydroxy-ethylamino)-ethan is replaced by the same quantity of any of the products which areobtainedby condensation in each case of 1 mol of 1:2-dichlorethane with2 mols of isopropanolamine, 1-hydroxy-2-amino-2-methylpropane or 1:3-dihydroxy-2 amino-2-methylpropane.

called condensed water (distilled water recovered from live steam) is tobe employed.

Example 1 2 parts of 1 :Z-di-(p-hydroxyethylamino) -ethane are mixedwith 1 part of the copper compound of the dyestuii which is obtained byphosgenation of 1 mol of 4-amino-4'-hydroxy-3'-carboxy-1:1'- azobenzeneand 1 mol of the condensation product of4-amino-2-methyl-5-methoxy-4'-hydroxy-3'-carboxy-1:1'-azobenzene-5-sulfonic acid with 4-nitrobenzoyl chlorideof which product the nitro group has been reduced to the amine.

With this dyestuff preparation cotton can be dyed for example in thefollowing manner:

3 parts of the dyestuflf preparation are covered with 200 parts of hotwater and the whole brought to the boil. From the stock solutionobtained there is prepared by dilution with water to 3000 parts byvolume and addition oi. Z'parts of anhydrous sodium carbonate, a dyebathinto which at about 60 C. are entered 100 parts of previously wettedcotton. Within hour the temperature is raised to boiling and it ismaintained for one hour at boiling temperature, during which after 5minutes and after 20 minutes boiling in each case 20 parts ofcrystalline sodium sulfate ar added.

After rinsing and drying of the cotton a yellow Similar dyeings areobtained when the copper compound is replaced by the nickel or cobaltcompound of the dyestufl initially mentioned.

Example 2 Equal parts are mixed of 1:2-di-(p-hydroxyethylamino)- ethaneand the copper compound of the dyestufi which is obtained as follows:

1 mol of the monoazo dyestufl from diazotized1-amino-4-hydroxy-5-carboxybenzene and 1- aminonaphthalene-I-sulfonicacid is diazotized and coupled with 1 mol of l-aminonaphthalene. Theamino compound obtained is again diazotized and coupled in an alkalinemedium with 1 mol of 2-amino-5-hydroxynaphthalene 7 sulfonic acid.

With this dyestufl preparation cotton can be dyed for example asfollows: I

2 parts of the dyestufl preparation are covere with 200 parts of waterand the whole brought to the boil. From this stock solution is preparedby dilution to 3000 parts by volume and addition of 2 parts of anhydroussodium carbonate, a dyebath into which at about 60 C. are entered partsof previously wetted cotton. Within $4; hour the temperature is raisedto boiling and the whole is maintained for 1 hour at boiling temperatureduring which after 5 minutes and after 20 minutes boiling in each case20 parts of crystalline sodium sulfate are added. The dyeing is rinsedin the cold, in which operation there iS advantageously added to thefinal rinsing bath 1 part of the condensation product which is obtainedwhen dicyandiamidine is heated with 4 times the quantity of 30 per cent.commercial formaldehyd for about 10 minutes to 100 C. and the dyeing isallowed to remain in this bath for about 5 minutes.

A blue dyeing results of excellent fastness to light and washing.

By employing instead of 1:2-di-(p-hydroxyethylamino) -ethane the basesmentioned in paragraph 5 of Example 1, equal results are obtained.

Example 3 Equal parts are mixed of 1:2-di-(p-hydroxyethylamino) -ethaneand the copper compound of the dyestufi' which is obtained as follows:

1 mol of l-(4'-amino-l:1'-diphenyl-4-)-3- methyl-pyrazolone-(S) isconverted by means of phosgene into the symmetrical urea derivative andthe latter is coupled with 1 mol of diazotizedl-amino-2-carboxybenzene-4-sulfonic acid.

With this dyestufl preparation cotton can be dyed for example asfollows:

3 parts of the dyestufi preparation are covered with 200 parts of hotwater and the whole brought to the boil. From the stock solutionobtained there is prepared by dilution with water to 3000 parts byvolume and addition of 2 parts of anhydrous sodium carbonate, a dyebathinto which at about 60 C. are entered 100 parts of previously wettedcotton. Within 4 hour the temperature is raised to boiling and the wholeis maintained for 1 hour at boiling temperature during which afterfollowing constitution Y After rinsing and drying of: the cotton a.yellow dyeing results of goodifastnesslto lightand washing.

. Example 4 2 parts -of 1:2 11i-(p-hydroxyethylaminolethane; 3'partsof-saccharose and tpartofthe copper compound of the dyestufi fromr'rnol'of tetrazotized 4 :4 -diamino'-3:3"- dihydroxy-1: 1

diphenyl and 2 mol'of 2-amino-5 hydroxynaphthalene-7-sulfonic acid, aremixed together.

With this dyestufl preparation cotton *can be dyed for exampleas'follows:

-dium carbonate; a dyebath into which at about 60 C. are entered 100partsof previously wetted cotton. "Within hour the temperature is raisedI 2 parts of thedyestufi preparation are covered with 200 parts of waterand the whole brought to the -boil.. From .the stock solution obtainedthere is prepared byidilution with 2800parts 'of water and additionvof 2parts. oLanhydrous sodium carbonate; a dyebath into whichat about 60 C.are entered 100. parts-of previouslywetted cotton. 'Within 14-hour thetemperature is raised to boiling. and theuwholeis maintained for 1 hourat boiling. temperature during which after 5 minutes and afterminutes-in each case- 20 parts of crystalline-sodium sulfate .are added.

After rinsing and. drying 'oither-cotton a blue dyeing is produced-=0!excellent fastness to' light and washing.

Prior. to drying' the dyeingzl can :be further treated in a bath ratioof1:30. ford/ 'hourat ordinary temperaturewith 4 per. cent of apreparation containing per- 100: parts-32 parts of a condensation:product =from dicyandiamidine and formaldehyde; -l1 parts of copperacetate,- 31' parts of sodium carbonateandam parts of ammonium chloride.The dyeing thus treated exhibits a "still further improved *fa'stness'to washing.

..E2ample 5 There'are mixed-together 2 parts of 1:2-di-(fi-hydroxyethylamino) -ethane with 1 part of-the copper compoundofthedyestuff whichisobtained by careful reduction with glucosein an alkalinemedi'um or the disa'zo' 'dye'stuff" of "the -With this fldyestufipreparation cotton can be "dyed for-example as'follows:

2 parts of the dyestufi preparation are covered witliZOO parts orhotwater and the whole brought to-theboil. *From-fthis-stocks'olution'there is preparedby dilution-"with water 'to"30001'parts by'volume-and addition"of 2-partsof-'anliydrous soto boiling and-the wholeis maintained for 1 hour at-boiling-temperature during which after 5minutes and after 20minutes boiling in each case 20 parts of crystallinesodium sulfate are added.

After rinsing and drying of the cotton a grey dyeing results of verygood fastness to light and washing.

Example 6 2*parts'of the dyestuff of the formula areintimately groundwith 4 parts of 1:2-di-(flhydroxyethylamino) -ethane and 1 part ofsodium copper tartrate.

3 parts of this preparation are dissolved in 200 parts of hot water andadded to a dyebath of 2800 parts of water and 2 parts of anhydroussodium carbonate. At about C. are entered parts The bath is dyeingpossesses a good'fastness to washing and an excellent fastness to light.

i using instead of the above dyestuif 2 parts of thedyestuif. of theformula -SO3H oonrcoon l 1103s NHGOC omooon a-preparationis obtainedwhich dyes cotton in navylblue shades fast to washing and light.

What we claim is:

1. Process for dyeing cellulosic materials whichcomprises carrying outthe dyeing with 2.

- metal.compound'diflicultly solubleper se of a direct dyeingazo'dyestu'ff which contains in complex union one 'of the metals withthe atomic numbers 27 to 29 in the presence of a solid base of thecomposition R1 CRH2 1i=(-"N'H(J-*CHT OH)2 wherein R1- stands for-amember selected from thegroup consisting of a hydrogen atom, an alkylgroupwith at-the most three carbon atoms and e'ahydroxymethyl. group, R2stands for a member selected from the group consisting of a hydrogenatom and a 'methyl group and n represents a whole-number up to 4.

2. Process for'dyeing cellulosic materials which comprises" carrying outthe 'dye'lng'with a metal compound dimcultlysolubleper se'of a directdyeing azo dyestuff which contains in complex union-one"-of--tl'1e"rhetdlswith" theatomic numaeeaeoe hers 27 to 29 in thepresence of the base correspondingtothe formula p a HOCH2-CH2-HN-CH2 I ICHhNH-CHQ-CHP-O A H 3. Process for dyeing cellulosic materials which v 1p 7. Process for dyeing cellulosic materials which comprises, carryingout the dyeing with the come '-p1ex copper compound of the dyestuflcorresponding to the formula H H? 0 B H0 SOIH H015 NH comprises carryingoutthe dyeingiwith a complex copper compound diflicultly soluble per seof a direct dyeing 'azo dyestufi in the presence of the basecorresponding to the formula 4. Process for dyeing vcellulosic materialswhich comprises carrying out the dyeing with the complex copper compoundof the dyestufl corre- 30 sponding to the formula HO M WLW CW in thepresence of the base corresponding to the formula 5. Process for dyeingcellulosic materials which I comprises carrying out the dyeing with thecomplex copper compound of the dyestufl correspending to the formula inthe presence of the base corresponding to the formula Ho cH1-crre-NH+cma8. Process for dyeing cellulosic materials which ,comprises carrying outthe dyeing with the dyestufi of the formula COOK in the presence ofsodium copper tartrate and of the base corresponding to the formula 9. Adyebath containing a metal compound dimcultly soluble per se of a directdyeing azo dyestufi which contains in complex union one of the metalswith the atomic numbers 27 to 29 and also containing a solid base of thecomposition wherein R1 stands for a member selected from in the presenceof the base corresponding to the formula HMHPCHZ-NH-CHQ- 6. Process fordyeing cellulosic materials which comprises carrying out the dyeing withthe complex copper compound of the dyestufl corresponding to the formulaCOOH Z i l C=N lHl in the presence of the base corresponding to theformula HO-CWNH-Cflrthe group consisting of a hydrogen atom, an

alkyl group with at the most three carbon atoms and a hydroxymethylgroup, Rx: stands for a member selected from the group consisting of ahydrogen atom and a methyl group and n represents a whole number up to4.

oo oc -i o-N-N om .Y 10. A dycbath containing a metal compounddifncultly soluble per se of a" dyeing azo dyestufi which contains incomplexunion one of C I-Ia-NHCH:CHz-OH the metals with the atomicnumbers 27 to 29 i i-seO Qs 11 and also containing the'basecorresponding to theformulap.

11. A dyebath containing a complex copper compound diflicultly solubleper-se-of' a direct dyeing azo dyestufi and also containingthe basecorresponding to the formula 12. A dyestufi preparation containing ametal compound, difllcultly, soluble; per per-f: :a direct:

dyeing azo dyestuif which contains in complex-:- union one of the metals.with ,the atomic hum-r bers,27 to 29 and alsoucontaining a solid baseof the composition R1 CH:,. =(-NH !ICHI:OH)L;

wherein R1 stands for a member selected from the group consisting of ahydrogen atom,-an alkyl 7 group with at the most three carbon atoms anda hydroxymethyl group, R1 stands for a member:

selected from the group consisting of'a hydrogen atom and a methyl groupand n represents a wholenumbereup to 4.1.

13. A dyestufl preparatiomcontaininga metal.

14.-A;-dyestufi preparation containing a com- 'plex copper compounddifficultly soluble per se of -a directadyeing azo dyestufi and alsocontaining thebase corresponding to the formula.

KAI MEN ZI. HENRI RIAT. J ACQUES'" WEGMANN.

References Cited in the file of this patent UNITED STATES PATENTS NameDate Straub Sept. '7, 1937 Number

1. PROCESS FOR DYEING CELLULOSIC MATERIALS WHICH COMPRISES CARRYING OUTTHE DYEING WITH A METAL COMPOUND DIFFICULTY SOLUBLE PER SE OF A DIRECTDYEING AZO DYESTUFF WHICH CONTAINS IN COMPLEX UNION ONE OF THE METALSWITH THE ATOMIC NUMBERS 27 TO 29 IN THE PRESENCE OF A SOLID BASE OF THECOMPOSITION